Improved source assessment of Si, Al and related mineral components to PM10 based on a daily sampling procedure

Samples obtained from an industrialized valley in the East Alpine region were collected daily for a half year and analyzed using X-ray fluorescence to examine the elements Si,Al,Fe,Ca,Mg,Na,K,Zn,P,S and Cl.Some factors affecting the changes of these elements were considered,including time,elemental correlations,weekday,weekend and seasonal changes.Diagnostic analysis provided an insight into a decoupling behavior that occursin siliceous and carbonates minerals.A decrease in Si and Al and an increase in carbonates,Na,K,Zn and P were observed during the cold season.However,a consistently high correlation of Si and Al was observed in all seasons.It was established that such high levels originated from street surface abrasion.The increase in variability and absolute levels of carbonates during the cold season was demonstrated by adding carbonates to the street surface as gritting material to increase the grip on snowy surfaces.A marked increase in Na and Cl was observed in winter which may have been caused by thaw salt that is widely used in winter in Austria.This was associated with a significant increase in K,Zn,and P in the cold season that was the result of domestic space heating with wood.PM10 levels in December were 12 μg/m3 and were higher than levels detected in July.It was established that such high levels originated from mineral oxides,wood smoke,and inorganic ionic material(s).     

Impact of mineral components and selected trace metals on ambient PM10 concentrations

PM10 levels of the mineral components Si, Al, Fe, Ca, Mg and some trace metals were measured at three different sites in the urban area of Vienna (Austria). Observed trace metal concentrations varied between less than 0.1 ng m^?3 (Cd) and approximately 200 ng m^?3 (Zn), mineral components showed enhanced concentrations ranging from 0.01 μg m^?3 (Ca) to 16.3 μg m^?3 (Si). The contribution of the respective mineral oxides to PM10 mass concentrations accounted on average for 26.4 ± 16% (n = 1090) of the PM10 mass, with enhanced rates in spring and autumn (monthly averages of up to 40%) and decreased contributions in the cold season (monthly averages below 10%). The atmospheric occurrence of Al, Ti and Sr could be assigned to crustal sources, whereas for the elements Ba, Ca, Fe, Mg, Mn and V an increased contribution of non-crustal origin was observed. PM10 levels of As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Sn and Zn were predominantly derived from man-made emissions. Intersite comparison indicated that urban PM10 mass concentrations and PM10 levels of As, Pb and Zn were predominantly influenced from the transport of aerosols from outside into the city, whereas for the elements Ba, Mg, Ca, Cu and Fe a distinctly increased impact of local emissions was observed. The contribution of these urban emissions to total PM10 concentrations was estimated by calculating the so-called “urban impact”, which was found to be 32.7 ± 18% (n = 392) in the case of PM10 mass concentrations. The investigated elements accounted on average for 31.3 ± 19% (n = 392) of the observed PM10 mass increase. The mean values for the “urban impacts” of individual elements varied between 25.5% (As) and 77.0% (Ba).     

Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

Polymerization of l-lactide with SnCl2: A Low Toxic and Eco-friendly Catalyst

Polymerizations of l-lactide catalyzed either by neat SnCl₂ or by SnCl₂?+?difunctional cocatalysts were conducted in bulk at 180, 160 and 140 °C with variation of the Lac/Cat ratio and time. With neat SnCl₂ poly(L-lactide) having weight average molecular weights (uncorrected M_w’s) up to 190 000 g mol^?1 were obtained mainly consisting of linear chains. Addition of salicylic acid or 1,1-bisphenol yielded a higher fraction of cyclic polylactides but lower molecular weights. Furthermore, SnCl₂ was compared with Bu₂SnCl₂ and various other metal chlorides and the best results were obtained with SnCl₂. With ethyl L-lactate as initiator SnCl₂-catalyzed ROPs were performed at 120 °C and the lac/initiator ratio was varied. All these experiments were conducted under conditions allowing for comparison with ROPs catalyzed with neat Sn(II)-2-ethyhexanoate. Such a comparison was also performed with ε-caprolactone as monomer.